CN109438410A - A kind of method of synthesizing ethylene carbonate - Google Patents
A kind of method of synthesizing ethylene carbonate Download PDFInfo
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- CN109438410A CN109438410A CN201811476900.8A CN201811476900A CN109438410A CN 109438410 A CN109438410 A CN 109438410A CN 201811476900 A CN201811476900 A CN 201811476900A CN 109438410 A CN109438410 A CN 109438410A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of method of synthesizing ethylene carbonate, this method carries out ester exchange reaction synthesizing ethylene carbonate as raw material using MgO/NaY as catalyst, using dimethyl carbonate (DMC) and ethylene glycol (EG).This method is easy to operate, and catalyst efficiency is high, and reclaimer is simple and multiplexing performance is good, and the production cost of synthesizing ethylene carbonate can be effectively reduced.
Description
Technical field
The present invention relates to a kind of preparation fields of carbonic ester, use molecular sieve catalyst carbonate synthesis second more particularly, to a kind of
The preparation method of enester.
Background technique
Ethylene carbonate is a kind of heterocyclic ketone, also known as 1,3- dioxane pentanone, ethylene carbonate or ethylene carbonate,
Abbreviation EC.Ethylene carbonate is more stable, only in the presence of metal oxide, silica gel, active carbon 200 DEG C can just decompose.Carbon
Vinyl acetate is the raw material of synthetic and surfactant, can be good at as the organic high boiling solvent of good polarity
Dissolve many polymer and resin.Printing and dyeing, plastics, gas separation, macromolecule are widely used in as a kind of organic intermediate simultaneously
Synthesis and the fields such as electrochemistry, alternative ethylene oxide are used for ethoxylation, can be used as synthesis furazolidone raw material and
It is used as fibre trimmer, waterglass system slurry and processing agent of other fibers etc., and is that carbonic acid is generated by ester-interchange method
The primary raw material of dimethyl ester, polycarbonate also acts as the high power lithium battery electrolyte of production high added value.In addition, with carbon
Acid esters is the fatty poly-ester carbonate of basic structural unit and it includes the copolymers of carbonate monomer as biodegradable
Material, oneself is increasingly caused the attention of scientist.Ethylene carbonate is mainly used as eyeball synthetic fibre, polyamide fibre, polyester, polyvinyl chloride resin etc.
Reel off raw silk from cocoons liquid, selective aromatics extractant, plastics and rubber intermediate foaming agent etc..In addition, the same propylene carbonate of ethylene carbonate
Rouge equally can be directly as sour gas (CO in de- natural gas2、H2S purifying solvent).And it can be taken with ethylene carbonate
For propylene phthalein amine, waterglass and urea system are referred and synthesized as soil quality stabilizing agent non-harmful in mixed mud engineering.In conclusion carbon
Vinyl acetate is widely used, and referred to as century green basic chemical industry raw material, market potential are huge.
The synthetic method of ethylene carbonate mainly includes phosgenation, ester-interchange method, halohydrin method, ethylene oxide and CO2It closes
Cheng Fa, alcoholysis of urea.
Phosgenation is the method for earliest preparation of industrialization ethylene carbonate.The technique is directly anti-using ethylene glycol and phosgene
It answers, but it is there are complex process, yield are low, at high cost, and phosgene has severe toxicity and generates serious pollution to environment, at present
Gradually eliminated.
Ethylene oxide and CO2Synthetic method is ethylene oxide and CO2With quaternary ammonium salt, Dawson heteropolyacid salt, Schiff
Aluminum complex, metal phthalocyanine are the synthetic method of dominant catalyst, and advantage is by greenhouse gases CO2Fixed synthesis, but should
Reaction is volume-diminished reaction, and condition of high voltage is conducive to the progress of reaction, so needing relatively severe condition, including needs complexity
Catalyst and higher reaction pressure.
Halohydrin method is halohydrin and CO2(or HCO3 -) CH under catalyst3The method of product is generated in CN solvent.
Raw material needed for this method and catalyst price are higher, severe reaction conditions, and yield is lower.
Currently used preparation method is that ester exchange reaction obtains ethylene carbonate.By the ester of dimethyl carbonate and ethylene glycol
Exchange reaction and the method for preparing ethylene carbonate is exactly ester-interchange method.The method is from the point of view of process and uncomplicated, it is important to can look for
To suitable catalyst.At present in the ester exchange reaction of dimethyl carbonate and ethylene glycol, common catalyst has metallic sodium, alcohol
The homogeneous base catalyst such as sodium, the homogeneous acid catalysts such as sulfuric acid, hydrochloric acid, but these homogeneous catalysts suffer from product separation it is difficult,
Catalyst reuse rate is low, is also easy to produce acid-base waste fluid etc. is difficult to the shortcomings that improving.Therefore, there is an urgent need to find a kind of operation letter
Single, high catalytic efficiency, catalyst repeat performance is good, is easy recycling, and the side of the low synthesizing ethylene carbonate of production cost
Method.
Summary of the invention
The technical problem to be solved by the present invention is to exchange carbonate synthesis ethylene for current dimethyl carbonate and glycol ester
The problems such as catalyst usage amount occurred during ester is big and separation and recovery of catalyst is difficult, and product yield is low, provides a kind of behaviour
Make simply, high catalytic efficiency, catalyst easily recycles, and catalyst reusability is good, the side of the low synthesizing ethylene carbonate of production cost
Method.
To solve the above-mentioned problems, present invention employs technical solutions below:
The method of synthesizing ethylene carbonate of the present invention is using MgO/NaY as catalyst, with dimethyl carbonate and second
Glycol is what raw material carried out.Wherein the molar ratio of oxide spinel dimethyl ester and ethylene glycol be 1:1~3:1, reaction temperature be 90~
120 DEG C, the reaction time is 2~12h.
Wherein the MgO/NaY solid base catalyst is prepared with the following method:
By Mg (NO3)2·6H2O is dissolved in deionized water, is then added thereto NaY molecular sieve, Mg (NO3)2·6H2O
Mass ratio with NaY is 1:5-1:0.5, and said mixture is stirred evenly, is impregnated at room temperature for 24 hours, is then done at 90 DEG C
Dry 4h, dry 2h at 120 DEG C, being finally putting into Muffle furnace at 550 DEG C and roasting 6h to get MgO load capacity is 3%-23%'s
MgO/NaY solid base catalyst.
As to another step restriction of the invention, MgO/NaY catalyst amount of the present invention is raw material ethylene glycol matter
The 5%~45% of amount.
The reaction process that MgO/NaY catalyzes and synthesizes ethylene carbonate is as follows:
Formula can be seen that the hydroxyl on the activation ethylene glycol of MgO/NaY first from the reactions above, form negative oxygen ion, then
Carbon ion on attack dimethyl carbonate, is connected on dimethyl carbonate, then takes off a methoxyl group, forms double bond, later
Activated hydroxyl groups form negative oxygen ion to MgO/NaY again, and attack carbon ion forms methoxyl group, takes off methoxyl group and obtains product carbon later
Vinyl acetate.
After above-mentioned technical solution, the present invention achieves the effect of highly significant, is catalysis with MgO/NaY solid base
Agent greatlys save energy consumption and cost in the synthesis process of ethylene carbonate, and the reaction time is shorter, and catalyst amount reduces, and urges
Agent catalytic performance is significant, and recycling using effect does not change significantly.
Detailed description of the invention
Fig. 1 is the XRD diagram before and after the use of MgO/NaY catalyst, and wherein A is that the XRD of freshly prepared MgO/NaY catalyst is composed
Figure, B are the XRD spectra using MgO/NaY catalyst after 4 times；
Fig. 2 is the CO before and after the use of MgO/NaY catalyst2- TPD figure, wherein A is freshly prepared MgO/NaY catalyst
CO2- TPD figure, B are the CO of MgO/NaY catalyst after evaluation is primary2- TPD figure, C are MgO/NaY catalyst after evaluation 4 times
CO2- TPD figure；
There is no significant changes using front-end geometry for MgO/NaY catalyst as can be seen from Figure 1；
From Fig. 2 illustrate basic sites property on four rear catalysts of dimethyl carbonate and glycol reaction system appraisal,
All there is no significant changes for intensity and quantity.These results illustrate MgO/NaY catalyst in dimethyl carbonate and ethylene glycol
The process stability for reacting synthesizing ethylene carbonate is very good.
Specific embodiment
The present invention will be described further with regard to following embodiment, however, it should be noted that these embodiments are only to illustrate
It is used, and is not necessarily to be construed as the limitation that the present invention is implemented.
MgO/NaY catalyst is prepared first: by Mg (NO3)2·6H2O is dissolved in deionized water, then by NaY molecular sieve
It is added thereto, Mg (NO3)2·6H2The mass ratio of O and NaY is 1:5-1:0.5, said mixture is stirred evenly, at room temperature
Dipping for 24 hours, the subsequent dry 4h at 90 DEG C, dry 2h at 120 DEG C, be finally putting into Muffle furnace at 550 DEG C roast 6h to get
MgO load capacity is the MgO/NaY solid base catalyst of 3%-23%.
The catalyst of above-mentioned preparation is used in following specific embodiments.
Embodiment 1
6mL dimethyl carbonate and 4mL ethylene glycol are added in flask, MgO/NaY is catalyst, and MgO load capacity is 5%,
Used catalyst amount is 1g, and reaction temperature is 90 DEG C, and reaction time 6h is reacted, ethylene carbonate at this point in the reaction
The yield of ester is 56.6%, and selectivity is 90.8%.
Embodiment 2
8mL dimethyl carbonate is added in flask and 4mL ethylene glycol, MgO/NaY are catalyst, MgO load capacity is
13%, used catalyst amount is 2g, and reaction temperature is 90 DEG C, and reaction time 6h is reacted, carbonic acid at this point in the reaction
The yield of vinyl acetate is 91.3%, and selectivity is 98.3%.
Embodiment 3
12mL dimethyl carbonate is added in flask and 4mL ethylene glycol, MgO/NaY are catalyst, MgO load capacity is
23%, used catalyst amount is 0.22g, and reaction temperature is 120 DEG C, and reaction time 8h is reacted at this point in the reaction,
The yield of ethylene carbonate is 47.9%, and selectivity is 99.1%.
Embodiment 4
18mL dimethyl carbonate is added in flask and 4mL ethylene glycol, MgO/NaY are catalyst, MgO load capacity is
10%, used catalyst amount is 2g, and reaction temperature is 90 DEG C, and reaction time 10h is reacted, carbon at this point in the reaction
The yield of vinyl acetate is 94.4%, and selectivity is 96.2%.
Embodiment 5
10mL dimethyl carbonate is added in flask and 4mL ethylene glycol, MgO/NaY are catalyst, MgO load capacity is
15%, used catalyst amount is 1.5g, and reaction temperature is 90 DEG C, and reaction time 9h is reacted, carbon at this point in the reaction
The yield of vinyl acetate is 92.8%, and selectivity is 98.7%.
Embodiment 6
6mL dimethyl carbonate is added in flask and 4mL ethylene glycol, MgO/NaY are catalyst, MgO load capacity is
20%, used catalyst amount is 1.5g, and reaction temperature is 90 DEG C, and reaction time 2h is reacted, carbon at this point in the reaction
The yield of vinyl acetate is 72.9%, and selectivity is 90.1%.
Embodiment 7
6mL dimethyl carbonate is added in flask and 4mL ethylene glycol, MgO/NaY are catalyst, MgO load capacity is
12%, used catalyst amount is 1.8g, and reaction temperature is 90 DEG C, and reaction time 9h is reacted, carbon at this point in the reaction
The yield of vinyl acetate is 82.8%, and selectivity is 99.2%.
Embodiment 8
By catalyst detergent, drying after the reaction of embodiment 4, it is used for circulation experiment, five times circulation experiment data to be as follows.
1. catalyst repeat performance evaluation result of table
As can be seen from the above table: catalyst prepared by the present invention still maintains preferable catalytic after five multiplexings
Energy.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (3)
1. a kind of method of synthesizing ethylene carbonate, it is characterised in that this method is using MgO/NaY as catalyst, using carbonic acid
Dimethyl ester and ethylene glycol are as raw material, and wherein the molar ratio of oxide spinel dimethyl ester and ethylene glycol is 1:1~3:1, reaction temperature
It is 90~120 DEG C, the reaction time is 2~12h.
2. a kind of method of synthesizing ethylene carbonate according to claim 1, it is characterised in that the MgO/NaY solid
Base catalyst is prepared with the following method:
By Mg (NO3)2·6H2O is dissolved in deionized water, is then added thereto NaY molecular sieve, Mg (NO3)2·6H2O and NaY
Mass ratio be 1:5-1:0.5, said mixture is stirred evenly, is impregnated at room temperature for 24 hours, then the dry 4h at 90 DEG C,
Dry 2h at 120 DEG C, is finally putting into Muffle furnace and roasts the MgO/NaY that 6h is 3%-23% to get MgO load capacity at 550 DEG C
Solid base catalyst.
3. a kind of method of synthesizing ethylene carbonate according to claim 1, it is characterised in that the MgO/NaY catalysis
Agent dosage is the 5%~45% of raw material quality of glycol.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478187A (en) * | 2022-02-21 | 2022-05-13 | 福州大学 | Process for coproducing methanol and ethylene carbonate through reaction and rectification |
| CN114751887A (en) * | 2022-04-21 | 2022-07-15 | 上海交通大学 | Synthetic method of cyclic ethane carbonic ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114478187A (en) * | 2022-02-21 | 2022-05-13 | 福州大学 | Process for coproducing methanol and ethylene carbonate through reaction and rectification |
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| CN114751887A (en) * | 2022-04-21 | 2022-07-15 | 上海交通大学 | Synthetic method of cyclic ethane carbonic ester |
| CN114751887B (en) * | 2022-04-21 | 2024-04-16 | 上海交通大学 | Synthesis method of ethylene carbonate |
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